organic compounds
(±)-3-Benzyloxy-1-(4-methoxybenzyl)piperidine-2-thione
aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, PO Wits 2050, Johannesburg, South Africa
*Correspondence e-mail: joseph.michael@wits.ac.za
The title molecule, C20H23NO2S, adopts a twisted conformation in which the two aromatic rings connected to the central piperidine ring are orientated trans to each other. An intramolecular C—H⋯S contact occurs. In the crystal, C—H⋯π and C—H⋯O interactions act to stabilize the structure in three dimensions.
Related literature
For the use of related piperidinethiones in the synthesis of febrifugine analogues, see: Michael et al. (2006). For information on the biological activity of febrifugine, see: Murata et al. (1998).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT-NT (Bruker, 2005); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812048854/go2079sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048854/go2079Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812048854/go2079Isup3.cml
The title compound was synthesized by heating a mixture of (3S)-3-benzyloxy-1-(4-methoxybenzyl)piperidin-2-one (170 mg, 0.52 mmol) and Lawesson's reagent (106 mg, 0.26 mmol) in benzene (8 ml) under reflux for 4 h. After evaporation of the solvent in vacuo, the residue was purified by
on silica gel with hexane/ethyl acetate (4:1 v/v) as to yield the racemic product as shiny colourless plates (174 mg, 98%), m.p. 349.5–351.5 K.All H atoms attached to carbon were positioned geometrically, and allowed to ride on their parent atoms, with C—H bond lengths of 0.95 Å (CH), 0.99 Å (CH2) or 0.98 Å (CH3), and isotropic displacement parameters set to 1.2 (CH and CH2) or 1.5 times (CH3) the Ueq of the parent atom.
The title piperidinethione was prepared as an intermediate for the total synthesis of febrifugine, a quinazoline alkaloid with potent antimalarial activity (Murata et al., 1998). Related thiolactam intermediates have been used in the synthesis of febrifugine analogues in ongoing investigations in our laboratories (Michael et al., 2006). It should be noted that, although an optically pure lactam was used in the synthesis of the title compound,
took place during the replacement of oxygen by sulfur with Lawesson's reagent.The title organic compound (Fig. 1) crystallizes in the π interactions involving the ring defined by C16—C21 are present in the structure while no such interactions exist for the aromatic ring defined by C8—C13. These two C—H···π interactions act to bring three molecules together which interact further through the C—H···O interaction as shown in Fig. 2. No significant π···π interactions are present in the structure.
Pbca. The molecule adopts a twisted conformation in which the two aromatic rings connected to the piperidine ring are orientated trans to each other. The aromatic rings are also rotated with respect to each other such that the angle between least squares planes defined by the two rings is 59.04 (6)°. The most significant weak interactions in this structure are listed in Table 1. Two C—H···For the use of related piperidinethiones in the synthesis of febrifugine analogues, see: Michael et al. (2006). For information on the biological activity of febrifugine, see: Murata et al. (1998).
Data collection: APEX2 (Bruker, 2005); cell
SAINT-NT (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).C20H23NO2S | F(000) = 1456 |
Mr = 341.45 | Dx = 1.275 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 978 reflections |
a = 18.371 (3) Å | θ = 2.5–28.0° |
b = 10.4844 (15) Å | µ = 0.19 mm−1 |
c = 18.467 (3) Å | T = 173 K |
V = 3556.9 (9) Å3 | Plate, colourless |
Z = 8 | 0.47 × 0.28 × 0.05 mm |
Bruker APEXII CCD area-detector diffractometer | 2949 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 28.0°, θmin = 2.2° |
phi and ω scans | h = −24→19 |
22717 measured reflections | k = −13→13 |
4286 independent reflections | l = −23→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5277P] where P = (Fo2 + 2Fc2)/3 |
4286 reflections | (Δ/σ)max = 0.003 |
218 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C20H23NO2S | V = 3556.9 (9) Å3 |
Mr = 341.45 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 18.371 (3) Å | µ = 0.19 mm−1 |
b = 10.4844 (15) Å | T = 173 K |
c = 18.467 (3) Å | 0.47 × 0.28 × 0.05 mm |
Bruker APEXII CCD area-detector diffractometer | 2949 reflections with I > 2σ(I) |
22717 measured reflections | Rint = 0.046 |
4286 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.26 e Å−3 |
4286 reflections | Δρmin = −0.26 e Å−3 |
218 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C2 | −0.00224 (8) | 0.06796 (14) | 0.61154 (8) | 0.0260 (3) | |
C3 | 0.02325 (8) | 0.19576 (13) | 0.58013 (8) | 0.0278 (3) | |
H3 | 0.0100 | 0.1991 | 0.5277 | 0.033* | |
C4 | 0.10388 (8) | 0.21947 (16) | 0.58763 (9) | 0.0339 (4) | |
H4A | 0.1153 | 0.3082 | 0.5733 | 0.041* | |
H4B | 0.1311 | 0.1611 | 0.5553 | 0.041* | |
C5 | 0.12655 (9) | 0.19740 (15) | 0.66565 (9) | 0.0371 (4) | |
H5A | 0.1790 | 0.2166 | 0.6715 | 0.045* | |
H5B | 0.0988 | 0.2548 | 0.6980 | 0.045* | |
C6 | 0.11198 (8) | 0.06000 (15) | 0.68586 (9) | 0.0339 (4) | |
H6A | 0.1511 | 0.0060 | 0.6654 | 0.041* | |
H6B | 0.1140 | 0.0518 | 0.7392 | 0.041* | |
C7 | 0.02107 (8) | −0.11296 (14) | 0.69241 (8) | 0.0310 (3) | |
H7A | −0.0293 | −0.1356 | 0.6782 | 0.037* | |
H7B | 0.0225 | −0.1057 | 0.7458 | 0.037* | |
C8 | 0.07247 (8) | −0.21843 (14) | 0.66849 (8) | 0.0265 (3) | |
C9 | 0.09864 (8) | −0.22570 (14) | 0.59808 (8) | 0.0293 (3) | |
H9 | 0.0846 | −0.1624 | 0.5640 | 0.035* | |
C10 | 0.14501 (8) | −0.32359 (14) | 0.57614 (8) | 0.0295 (3) | |
H10 | 0.1621 | −0.3273 | 0.5276 | 0.035* | |
C11 | 0.16592 (8) | −0.41589 (14) | 0.62622 (9) | 0.0311 (3) | |
C12 | 0.13904 (9) | −0.41094 (14) | 0.69669 (9) | 0.0353 (4) | |
H12 | 0.1522 | −0.4751 | 0.7306 | 0.042* | |
C13 | 0.09325 (9) | −0.31299 (14) | 0.71751 (9) | 0.0324 (4) | |
H13 | 0.0757 | −0.3100 | 0.7659 | 0.039* | |
C14 | 0.23736 (9) | −0.52714 (17) | 0.53823 (10) | 0.0434 (4) | |
H14A | 0.1953 | −0.5379 | 0.5061 | 0.065* | |
H14B | 0.2693 | −0.6017 | 0.5342 | 0.065* | |
H14C | 0.2643 | −0.4503 | 0.5243 | 0.065* | |
C15 | −0.02311 (8) | 0.40960 (13) | 0.58316 (9) | 0.0293 (3) | |
H15A | −0.0249 | 0.3973 | 0.5300 | 0.035* | |
H15B | 0.0205 | 0.4611 | 0.5948 | 0.035* | |
C16 | −0.09058 (8) | 0.47794 (13) | 0.60827 (8) | 0.0256 (3) | |
C17 | −0.15243 (8) | 0.41094 (14) | 0.62983 (8) | 0.0300 (3) | |
H17 | −0.1518 | 0.3203 | 0.6303 | 0.036* | |
C18 | −0.21487 (9) | 0.47569 (15) | 0.65056 (9) | 0.0359 (4) | |
H18 | −0.2567 | 0.4292 | 0.6654 | 0.043* | |
C19 | −0.21667 (9) | 0.60777 (16) | 0.64975 (9) | 0.0373 (4) | |
H19 | −0.2596 | 0.6518 | 0.6640 | 0.045* | |
C20 | −0.15566 (9) | 0.67528 (15) | 0.62815 (9) | 0.0351 (4) | |
H20 | −0.1569 | 0.7658 | 0.6270 | 0.042* | |
C21 | −0.09291 (8) | 0.61116 (14) | 0.60820 (8) | 0.0303 (3) | |
H21 | −0.0510 | 0.6582 | 0.5943 | 0.036* | |
N1 | 0.04038 (6) | 0.01121 (11) | 0.66005 (6) | 0.0267 (3) | |
S1 | −0.08302 (2) | 0.01240 (4) | 0.58307 (2) | 0.03658 (12) | |
O1 | 0.21278 (6) | −0.51478 (10) | 0.61136 (7) | 0.0413 (3) | |
O2 | −0.01884 (6) | 0.28903 (9) | 0.61845 (5) | 0.0299 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0271 (8) | 0.0236 (7) | 0.0273 (8) | 0.0015 (6) | 0.0041 (6) | −0.0019 (6) |
C3 | 0.0297 (8) | 0.0245 (7) | 0.0293 (8) | 0.0041 (6) | 0.0051 (6) | 0.0001 (6) |
C4 | 0.0289 (8) | 0.0281 (8) | 0.0447 (10) | 0.0004 (6) | 0.0072 (7) | 0.0032 (7) |
C5 | 0.0297 (9) | 0.0303 (9) | 0.0514 (10) | −0.0019 (7) | −0.0028 (7) | −0.0028 (7) |
C6 | 0.0296 (8) | 0.0319 (8) | 0.0402 (9) | −0.0004 (7) | −0.0079 (7) | −0.0001 (7) |
C7 | 0.0320 (8) | 0.0288 (8) | 0.0321 (8) | 0.0011 (6) | 0.0032 (7) | 0.0063 (6) |
C8 | 0.0274 (8) | 0.0219 (7) | 0.0303 (8) | −0.0025 (6) | −0.0027 (6) | 0.0021 (6) |
C9 | 0.0318 (8) | 0.0239 (7) | 0.0322 (8) | −0.0015 (6) | −0.0036 (6) | 0.0049 (6) |
C10 | 0.0311 (8) | 0.0270 (8) | 0.0303 (8) | −0.0038 (6) | −0.0010 (6) | −0.0019 (6) |
C11 | 0.0304 (8) | 0.0228 (8) | 0.0402 (9) | 0.0001 (6) | −0.0102 (7) | −0.0045 (6) |
C12 | 0.0468 (10) | 0.0243 (8) | 0.0348 (9) | 0.0027 (7) | −0.0128 (7) | 0.0044 (7) |
C13 | 0.0413 (9) | 0.0277 (8) | 0.0282 (8) | −0.0028 (7) | −0.0036 (7) | 0.0030 (6) |
C14 | 0.0348 (9) | 0.0402 (10) | 0.0552 (11) | 0.0066 (7) | −0.0036 (8) | −0.0135 (8) |
C15 | 0.0287 (8) | 0.0220 (7) | 0.0371 (9) | 0.0003 (6) | 0.0033 (6) | 0.0049 (6) |
C16 | 0.0258 (7) | 0.0222 (7) | 0.0290 (7) | −0.0001 (6) | −0.0030 (6) | 0.0012 (6) |
C17 | 0.0298 (8) | 0.0212 (7) | 0.0390 (9) | −0.0024 (6) | −0.0011 (6) | 0.0005 (6) |
C18 | 0.0261 (8) | 0.0327 (9) | 0.0488 (10) | −0.0036 (7) | 0.0016 (7) | 0.0014 (7) |
C19 | 0.0308 (9) | 0.0337 (9) | 0.0473 (10) | 0.0083 (7) | 0.0001 (7) | −0.0015 (7) |
C20 | 0.0404 (10) | 0.0209 (8) | 0.0440 (10) | 0.0037 (7) | −0.0011 (7) | −0.0001 (7) |
C21 | 0.0314 (8) | 0.0239 (8) | 0.0356 (8) | −0.0043 (6) | 0.0001 (6) | 0.0024 (6) |
N1 | 0.0265 (6) | 0.0233 (6) | 0.0303 (7) | 0.0009 (5) | 0.0005 (5) | 0.0009 (5) |
S1 | 0.0307 (2) | 0.0367 (2) | 0.0423 (2) | −0.00675 (17) | −0.00588 (17) | 0.00665 (18) |
O1 | 0.0433 (7) | 0.0328 (6) | 0.0479 (7) | 0.0116 (5) | −0.0118 (5) | −0.0078 (5) |
O2 | 0.0343 (6) | 0.0235 (5) | 0.0318 (6) | 0.0065 (4) | 0.0075 (5) | 0.0037 (4) |
C2—N1 | 1.3302 (19) | C11—O1 | 1.3752 (19) |
C2—C3 | 1.533 (2) | C11—C12 | 1.393 (2) |
C2—S1 | 1.6788 (15) | C12—C13 | 1.382 (2) |
C3—O2 | 1.4334 (17) | C12—H12 | 0.9500 |
C3—C4 | 1.509 (2) | C13—H13 | 0.9500 |
C3—H3 | 1.0000 | C14—O1 | 1.430 (2) |
C4—C5 | 1.518 (2) | C14—H14A | 0.9800 |
C4—H4A | 0.9900 | C14—H14B | 0.9800 |
C4—H4B | 0.9900 | C14—H14C | 0.9800 |
C5—C6 | 1.512 (2) | C15—O2 | 1.4244 (17) |
C5—H5A | 0.9900 | C15—C16 | 1.505 (2) |
C5—H5B | 0.9900 | C15—H15A | 0.9900 |
C6—N1 | 1.4897 (19) | C15—H15B | 0.9900 |
C6—H6A | 0.9900 | C16—C17 | 1.394 (2) |
C6—H6B | 0.9900 | C16—C21 | 1.397 (2) |
C7—N1 | 1.4756 (18) | C17—C18 | 1.387 (2) |
C7—C8 | 1.520 (2) | C17—H17 | 0.9500 |
C7—H7A | 0.9900 | C18—C19 | 1.385 (2) |
C7—H7B | 0.9900 | C18—H18 | 0.9500 |
C8—C9 | 1.388 (2) | C19—C20 | 1.384 (2) |
C8—C13 | 1.396 (2) | C19—H19 | 0.9500 |
C9—C10 | 1.394 (2) | C20—C21 | 1.384 (2) |
C9—H9 | 0.9500 | C20—H20 | 0.9500 |
C10—C11 | 1.393 (2) | C21—H21 | 0.9500 |
C10—H10 | 0.9500 | ||
N1—C2—C3 | 117.77 (13) | O1—C11—C10 | 124.33 (15) |
N1—C2—S1 | 125.17 (12) | C12—C11—C10 | 119.78 (14) |
C3—C2—S1 | 117.04 (11) | C13—C12—C11 | 120.22 (14) |
O2—C3—C4 | 111.83 (12) | C13—C12—H12 | 119.9 |
O2—C3—C2 | 104.16 (11) | C11—C12—H12 | 119.9 |
C4—C3—C2 | 114.15 (12) | C12—C13—C8 | 120.93 (15) |
O2—C3—H3 | 108.8 | C12—C13—H13 | 119.5 |
C4—C3—H3 | 108.8 | C8—C13—H13 | 119.5 |
C2—C3—H3 | 108.8 | O1—C14—H14A | 109.5 |
C3—C4—C5 | 109.36 (13) | O1—C14—H14B | 109.5 |
C3—C4—H4A | 109.8 | H14A—C14—H14B | 109.5 |
C5—C4—H4A | 109.8 | O1—C14—H14C | 109.5 |
C3—C4—H4B | 109.8 | H14A—C14—H14C | 109.5 |
C5—C4—H4B | 109.8 | H14B—C14—H14C | 109.5 |
H4A—C4—H4B | 108.3 | O2—C15—C16 | 109.08 (12) |
C6—C5—C4 | 109.33 (13) | O2—C15—H15A | 109.9 |
C6—C5—H5A | 109.8 | C16—C15—H15A | 109.9 |
C4—C5—H5A | 109.8 | O2—C15—H15B | 109.9 |
C6—C5—H5B | 109.8 | C16—C15—H15B | 109.9 |
C4—C5—H5B | 109.8 | H15A—C15—H15B | 108.3 |
H5A—C5—H5B | 108.3 | C17—C16—C21 | 118.62 (14) |
N1—C6—C5 | 113.86 (13) | C17—C16—C15 | 121.30 (13) |
N1—C6—H6A | 108.8 | C21—C16—C15 | 120.05 (13) |
C5—C6—H6A | 108.8 | C18—C17—C16 | 120.43 (14) |
N1—C6—H6B | 108.8 | C18—C17—H17 | 119.8 |
C5—C6—H6B | 108.8 | C16—C17—H17 | 119.8 |
H6A—C6—H6B | 107.7 | C19—C18—C17 | 120.40 (15) |
N1—C7—C8 | 112.02 (12) | C19—C18—H18 | 119.8 |
N1—C7—H7A | 109.2 | C17—C18—H18 | 119.8 |
C8—C7—H7A | 109.2 | C20—C19—C18 | 119.67 (15) |
N1—C7—H7B | 109.2 | C20—C19—H19 | 120.2 |
C8—C7—H7B | 109.2 | C18—C19—H19 | 120.2 |
H7A—C7—H7B | 107.9 | C19—C20—C21 | 120.17 (15) |
C9—C8—C13 | 118.27 (14) | C19—C20—H20 | 119.9 |
C9—C8—C7 | 121.82 (13) | C21—C20—H20 | 119.9 |
C13—C8—C7 | 119.89 (13) | C20—C21—C16 | 120.71 (14) |
C8—C9—C10 | 121.62 (14) | C20—C21—H21 | 119.6 |
C8—C9—H9 | 119.2 | C16—C21—H21 | 119.6 |
C10—C9—H9 | 119.2 | C2—N1—C7 | 121.73 (13) |
C11—C10—C9 | 119.16 (14) | C2—N1—C6 | 125.56 (13) |
C11—C10—H10 | 120.4 | C7—N1—C6 | 112.68 (12) |
C9—C10—H10 | 120.4 | C11—O1—C14 | 117.04 (13) |
O1—C11—C12 | 115.88 (14) | C15—O2—C3 | 114.16 (11) |
N1—C2—C3—O2 | −101.85 (14) | C21—C16—C17—C18 | 0.2 (2) |
S1—C2—C3—O2 | 76.83 (14) | C15—C16—C17—C18 | −177.91 (15) |
N1—C2—C3—C4 | 20.40 (19) | C16—C17—C18—C19 | 0.3 (2) |
S1—C2—C3—C4 | −160.92 (11) | C17—C18—C19—C20 | −0.1 (3) |
O2—C3—C4—C5 | 67.16 (16) | C18—C19—C20—C21 | −0.7 (3) |
C2—C3—C4—C5 | −50.78 (17) | C19—C20—C21—C16 | 1.2 (2) |
C3—C4—C5—C6 | 62.00 (17) | C17—C16—C21—C20 | −0.9 (2) |
C4—C5—C6—N1 | −43.34 (18) | C15—C16—C21—C20 | 177.18 (14) |
N1—C7—C8—C9 | −39.1 (2) | C3—C2—N1—C7 | −178.97 (12) |
N1—C7—C8—C13 | 142.40 (14) | S1—C2—N1—C7 | 2.5 (2) |
C13—C8—C9—C10 | −0.6 (2) | C3—C2—N1—C6 | −1.2 (2) |
C7—C8—C9—C10 | −179.13 (14) | S1—C2—N1—C6 | −179.75 (12) |
C8—C9—C10—C11 | −0.4 (2) | C8—C7—N1—C2 | 112.23 (15) |
C9—C10—C11—O1 | −178.26 (14) | C8—C7—N1—C6 | −65.82 (16) |
C9—C10—C11—C12 | 1.5 (2) | C5—C6—N1—C2 | 13.5 (2) |
O1—C11—C12—C13 | 178.11 (14) | C5—C6—N1—C7 | −168.55 (13) |
C10—C11—C12—C13 | −1.7 (2) | C12—C11—O1—C14 | 175.93 (13) |
C11—C12—C13—C8 | 0.7 (2) | C10—C11—O1—C14 | −4.3 (2) |
C9—C8—C13—C12 | 0.4 (2) | C16—C15—O2—C3 | 155.93 (12) |
C7—C8—C13—C12 | 179.00 (14) | C4—C3—O2—C15 | 76.17 (15) |
O2—C15—C16—C17 | −29.49 (19) | C2—C3—O2—C15 | −160.07 (12) |
O2—C15—C16—C21 | 152.48 (13) |
Cg1 is the centroid of the C16–C21 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···S1 | 0.99 | 2.54 | 3.0760 (16) | 114 |
C13—H13···O2i | 0.95 | 2.59 | 3.4913 (19) | 158 |
C6—H6B···Cg1i | 0.99 | 2.54 | 3.5066 (19) | 165 |
C14—H14A···Cg1ii | 0.98 | 2.61 | 3.455 (2) | 144 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C20H23NO2S |
Mr | 341.45 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 18.371 (3), 10.4844 (15), 18.467 (3) |
V (Å3) | 3556.9 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.47 × 0.28 × 0.05 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22717, 4286, 2949 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.01 |
No. of reflections | 4286 |
No. of parameters | 218 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.26 |
Computer programs: APEX2 (Bruker, 2005), SAINT-NT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and SCHAKAL99 (Keller, 1999), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Cg1 is the centroid of the C16–C21 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···S1 | 0.99 | 2.54 | 3.0760 (16) | 114 |
C13—H13···O2i | 0.95 | 2.59 | 3.4913 (19) | 158 |
C6—H6B···Cg1i | 0.99 | 2.54 | 3.5066 (19) | 165 |
C14—H14A···Cg1ii | 0.98 | 2.61 | 3.455 (2) | 144 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, −y, −z+1. |
Acknowledgements
This work was supported by the University of the Witwatersrand and the National Research Foundation, Pretoria (grant number 78837).
References
Bruker (2005). APEX2 and SAINT-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Keller, E. (1999). SCHAKAL99. University of Freiberg, Germany. Google Scholar
Michael, J. P., de Koning, C. B. & Pienaar, D. P. (2006). Synlett, pp. 383–386. Web of Science CrossRef Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title piperidinethione was prepared as an intermediate for the total synthesis of febrifugine, a quinazoline alkaloid with potent antimalarial activity (Murata et al., 1998). Related thiolactam intermediates have been used in the synthesis of febrifugine analogues in ongoing investigations in our laboratories (Michael et al., 2006). It should be noted that, although an optically pure lactam was used in the synthesis of the title compound, racemization took place during the replacement of oxygen by sulfur with Lawesson's reagent.
The title organic compound (Fig. 1) crystallizes in the space group Pbca. The molecule adopts a twisted conformation in which the two aromatic rings connected to the piperidine ring are orientated trans to each other. The aromatic rings are also rotated with respect to each other such that the angle between least squares planes defined by the two rings is 59.04 (6)°. The most significant weak interactions in this structure are listed in Table 1. Two C—H···π interactions involving the ring defined by C16—C21 are present in the structure while no such interactions exist for the aromatic ring defined by C8—C13. These two C—H···π interactions act to bring three molecules together which interact further through the C—H···O interaction as shown in Fig. 2. No significant π···π interactions are present in the structure.